High wet fast disperse dye mixtures of n-[4-(5-fluoro-2,4-dinitro-phenylazo)-phenyl]-amine derivatives and n-[4-(4-nitro-phenylazo)-phenyl]-amine derivatives

ABSTRACT

The present invention is directed to dye mixtures comprising dyes of formula (1) and dyes of formula (2), the process of the production and the use of the dye mixtures.

This invention relates to high wet fast disperse azo dye mixtures.

Disperse-azo-dyes (1) with the substitution pattern 2,4,5-in thediazo-component are known e.g. from GB 2 020 680, U.S. Pat. No.4,379,819, WO 2005/056690, WO 2005/040283 and WO 2016/041849. Dyes withgeneral Structure (2) and their mixtures are also known,—e.g. from EP 0864 615, EP 0 894 830, EP 0 555 179 and WO 2002/081572, but they haveunsatisfactory build up properties for deeper shades and/or insufficientwash- and contact-fastnesses.

It was now found that certain combinations of azo dyes of the formula(1) together with dyes of formula (2) result in improved build up andgood wash- and contact-fastness properties on polyester and polyesterblends especially on polyester-elastane/polyester-spandex.

The present invention thus is directed to a dye mixture comprising

at least one dye of formula (1)

wherein independent of each otherR¹ is hydrogen, (C₁-C₄)-alkyl or (C₁-C₄)-alkoxy,R² is hydrogen, carboxy, (C₁-C₄)-alkyl, halogen, acylamino, —NHCO-aryl,—NHCO-benzyl or sulfonylamino,R³ and R⁴ is hydrogen, (C₁-C₄)-alkyl, (CH₂)_(n)-phenyl, CH₂—CH═CH₂,(CH₂)_(n)—OH, (CH₂)_(n)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O-phenyl,(CH₂)_(n)—O-benzyl, (CH₂)_(n)—O—(CH₂)_(m)—OH,(CH₂)_(n)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O—(CH₂)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COOH,(CH₂)_(n)—COO—(C₁-C₄)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₄)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, CHR⁹—(CH₂)_(p)—(C₁-C₄)-alkyl,CHR⁹—(CH₂)_(p) phenyl, CHR⁹—CH═CH₂, CHR⁹—(CH₂)_(p)—OH,CHR⁹—(CH₂)_(p)—O—(C₁-C₄)-alkyl, CHR⁹—(CH₂)_(p)—O-phenyl,CHR⁹—(CH₂)_(p)—O-benzyl, CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—OH,CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl,CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl, CHR⁹—(CH₂)_(p)—COOH,CHR⁹—(CH₂)_(p)—COO—(C₁-C₄)-alkyl, CHR⁹—(CH₂)_(p)—COO-phenyl,CHR⁹—(CH₂)_(p)—COO-benzyl, CHR⁹—(CH₂)_(p)—CN,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,CHR⁹—(CH₂)_(p)—O—CO—(C₁-C₄)-alkyl, CHR⁹—(CH₂)_(p)—O—CO-phenyl,CHR⁹—(CH₂)_(p)—O—CO-benzyl, CHR⁹—(CH₂)_(p)-2-furfuryl orCHR⁹—(CH₂)_(p)—O—(CH₂)_(n)-2-furfuryl,

-   -   wherein    -   R⁹ is (C₁-C₄)-alkyl or (C₁-C₄)-alkyl substituted by —OH or        halogen,    -   n is 1 to 4,    -   m is 1 to 4 and    -   p is 0 to 3,        with the proviso that at least one of R³ and R⁴ is not hydrogen,        and        at least one dye of formula (2)

wherein independent of each otherR⁵ and R⁶ is hydrogen, (C₁-C₄)-alkyl, (CH₂)_(n)-phenyl, CH₂—CH═CH₂,(CH₂)_(n)—OH, (CH₂)_(n)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O-phenyl,(CH₂)_(n)—O-benzyl, (CH₂)_(n)—O—(CH₂)_(m)—OH,(CH₂)_(n)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O—(CH₂)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COOH,(CH₂)_(n)—COO—(C₁-C₄)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₄)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl or(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,

-   -   wherein    -   n is 1 to 4 and    -   m is 1 to 4,        with the proviso that at least one of R⁵ and R⁶ is not hydrogen,        R¹⁰ is hydrogen, (C₁-C₄)-alkyl or (C₁-C₄)-alkoxy,        R¹¹ is hydrogen, carboxy, (C₁-C₄)-alkyl, halogen, acylamino,        —NHCO-aryl, —NHCO-benzyl or sulfonylamino,        X⁵ and X⁶ is hydrogen, halogen, nitro or cyano,        with the proviso that at least one of X⁵ and X⁶ is not hydrogen.

Regarding both, dyes of formula (1) as well as dyes of formula (2),there exist preferred ones to form overall preferred combinations:

As to the selection of dyes of formula (1) a dye mixture as describedabove is preferred, wherein independent of each other in the at leastone dye of formula (1)

R¹ is hydrogen, methyl or methoxy,R² is hydrogen, hydroxy, COOH, COO—(C₁-C₂)-alkyl, (C₁-C₂)-alkyl,—NHCO—(C₁-C₂)-alkyl, —NHCO-aryl, —NHCO-benzyl or —NHSO₂—(C₁-C₂)-alkyl,R³ and R⁴ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)₂—O—(CH₂)_(m)—O-phenyl,(CH₂)₂—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, CHR⁹—CH═CH₂,CHR⁹—(CH₂)_(p)—O—(C₁-C₂)-alkyl, CHR⁹—(CH₂)_(p)—O-phenyl,CHR⁹—(CH₂)_(p)—O-benzyl, CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl, CHR⁹—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,CHR⁹—(CH₂)_(p)—COO-phenyl, CHR⁹—(CH₂)_(p)—COO-benzyl, CHR⁹—(CH₂)_(p)—CN,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,CHR⁹—(CH₂)_(p)—O—CO—(C₁-C₂)-alkyl, CHR⁹—(CH₂)_(p)—O—CO-phenyl orCHR⁹—(CH₂)_(p)—O—CO-benzyl,

-   -   wherein    -   R⁹ is (C₁-C₄)-alkyl or (C₁-C₄)-alkyl substituted by —OH or        halogen,    -   n is 1 or 2,    -   m is 1 or 2 and    -   p is 0 or 1,        with the proviso that at least one of R³ and R⁴ is not hydrogen.

More preferred is a dye mixture as described above, wherein independentof each other in the at least one dye of formula (1)

R¹ is hydrogen or methoxy,R² is hydrogen, methyl or —NHCO—(C₁-C₂)-alkyl,R³ and R⁴ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,CHR⁹—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,

-   -   wherein    -   R⁹ is (C₁-C₄)-alkyl    -   n is 1 or 2,    -   m is 1 or 2 and        with the proviso that at least one of R³ and R⁴ is not hydrogen.

A dye mixture as described above, wherein the at least one dye offormula (1) is a dye of formula (1a)

wherein independent from each otherR³ and R⁴ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl orCHR⁹—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,

-   -   wherein    -   R⁹ is (C₁-C₄)-alkyl,    -   n is 1 or 2,    -   m is 1 or 2 and    -   p is 0 or 1,        with the proviso that at least one of R³ and R⁴ is not hydrogen        and        R⁷ and R⁸ is ethyl or methyl,        forms a preferred embodiment of the present invention.

A dye mixture as described above, wherein the at least one dye offormula (1) is a dye of formula (1b)

wherein independent from each otherR³ and R⁴ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl orCHR⁹—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,

-   -   wherein    -   R⁹ is (C₁-C₄)-alkyl,    -   n is 1 or 2,    -   m is 1 or 2 and    -   p is 0 or 1,        with the proviso that at least one of R³ and R⁴ is not hydrogen        and        R⁷ is ethyl or methyl,        forms a preferred embodiment of the present invention.

A dye mixture as described above, wherein the at least one dye offormula (1) is a dye of formula (1c)

wherein independent from each otherR³ and R⁴ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl orCHR⁹—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,

-   -   wherein    -   R⁹ is (C₁-C₄)-alkyl,    -   n is 1 or 2,    -   m is 1 or 2 and    -   p is 0 or 1,        with the proviso that at least one of R³ and R⁴ is not hydrogen,        forms yet another preferred embodiment of the present invention.

Most preferred is a dye mixture as described above, wherein the at leastone dye of formula (1) is selected from the group consisting of

As to the selection of dyes of formula (2) a dye mixture as describedabove is preferred, wherein independent of each other in the at leastone dye of formula (2)

R⁵ and R⁶ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)₂—O—(CH₂)_(m)—O-phenyl,(CH₂)₂—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl or(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,

-   -   wherein    -   n is 1 or 2 and    -   m is 1 or 2,        with the proviso that at least one of R⁵ and R⁶ is not hydrogen,        R¹⁰ is hydrogen, methyl or methoxy,        R¹¹ is hydrogen, hydroxy, COOH, COO—(C₁-C₂)-alkyl,        (C₁-C₂)-alkyl, —NHCO—(C₁-C₂)-alkyl, —NHCO-aryl, —NHCO-benzyl or        —NHSO₂—(C₁-C₂)-alkyl and        X⁵ and X⁶ is hydrogen, chloro, bromo, nitro or cyano,        with the proviso that at least one of X⁵ and X⁶ is not hydrogen.

More preferred is a dye mixture as described above, wherein independentof each other in the at least one dye of formula (2)

R⁵ and R⁶ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,

-   -   wherein    -   n is 1 or 2 and    -   m is 1 or 2,        with the proviso that at least one of R⁵ and R⁶ is not hydrogen,        R¹⁰ is hydrogen or methoxy,        R¹¹ is hydrogen, methyl or —NHCO—(C₁-C₂)-alkyl and        X⁵ and X⁶ is hydrogen, bromo, chloro, nitro or cyano,        with the proviso that at least one of X⁵ and X⁶ is not hydrogen.

A dye mixture as described above, wherein the at least one dye offormula (2) is a dye of formula (2a)

wherein independent from each otherR⁵ and R⁶ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,

-   -   wherein    -   n is 1 or 2 and    -   m is 1 or 2,        with the proviso that at least one of R⁵ and R⁶ is not hydrogen,        R⁷ and R⁸ is ethyl or methyl,        X⁵ is hydrogen, bromo, chloro, nitro or cyano and        X⁶ is nitro or cyano,        with the proviso that X⁵ and X⁶ are not both nitro,        forms a preferred embodiment of the present invention.

A dye mixture as described above, wherein the at least one dye offormula (2) is a dye of formula (2b)

R⁵ and R⁶ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,

-   -   wherein    -   n is 1 or 2 and    -   m is 1 or 2,        with the proviso that at least one of R⁵ and R⁶ is not hydrogen,        R⁷ is ethyl or methyl and        X⁵ is bromo, chloro, nitro or cyano and        X⁶ is nitro or cyano,        with the proviso that X⁵ and X⁶ are not both nitro        forms another preferred embodiment of the present invention.

A dye mixture as described above, wherein the at least one dye offormula (2) is a dye of formula (2c)

wherein independent from each otherR² is hydrogen or —NHCO—(C₁-C₂)-alkyl,R⁵ and R⁶ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,

-   -   wherein    -   n is 1 or 2 and    -   m is 1 or 2        with the proviso that at least one of R⁵ and R⁶ is not hydrogen,        X⁵ and X⁶ is bromo or chloro        forms yet another preferred embodiment of the present invention.

A dye mixture as described above, wherein the at least one dye offormula (2) is a dye of formula (2d)

wherein independent from each otherR⁵ and R⁶ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,

-   -   wherein    -   n is 1 or 2 and    -   m is 1 or 2        with the proviso that at least one of R⁵ and R⁶ is not hydrogen,        R⁷ is ethyl or methyl and        X⁶ is chloro, bromo, nitro or cyano        forms still another preferred embodiment of the present        invention.

Most preferred is a dye mixture as described above, wherein the at leastone dye of formula (2) is selected from the group consisting of

Also, regarding the number of different dyes selected from the onesshown above there exist preferred dye mixtures:

Preferred are dye mixtures comprising one dye of formula (1) and one dyeof formula (2).

Preferred are dye mixtures comprising two dyes of formula (1) and onedye of formula (2).

Preferred are dye mixtures comprising one dye of formula (1) and twodyes of formula (2).

And preferred are dye mixtures comprising two dyes of formula (1) andtwo dyes of formula (2).

Those dye mixtures as described above are particularly preferred,wherein preferred dyes of formula (1) and preferred dyes of formula (2)are combined, such as a dye mixture, wherein independent from each other

R¹ is hydrogen, methyl or methoxy,R² is hydrogen, hydroxy, COOH, COO—(C₁-C₂)-alkyl, (C₁-C₂)-alkyl,—NHCO—(C₁-C₂)-alkyl, —NHCO-aryl, —NHCO-benzyl or —NHSO₂—(C₁-C₂)-alkyl,R³ to R⁶ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)₂—O—(CH₂)_(m)—O-phenyl,(CH₂)₂—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl or(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,

-   -   wherein    -   n is 1 or 2 and    -   m is 1 or 2,        with the proviso that at least one of R³ and R⁴ in formula (1)        and at least one of R⁵ and R⁶ in formula (2) is not hydrogen,        R¹⁰ is hydrogen, methyl or methoxy,        R¹¹ is hydrogen, hydroxy, COOH, COO—(C₁-C₂)-alkyl,        (C₁-C₂)-alkyl, —NHCO—(C₁-C₂)-alkyl, —NHCO-aryl, —NHCO-benzyl or        —NHSO₂—(C₁-C₂)-alkyl and        X⁵ and X⁶ is hydrogen, chloro, bromo, nitro or cyano,        with the proviso that at least one of X⁵ and X⁶ in formula (2)        is not hydrogen.

Accordingly, even more preferred is a dye mixture as described above,wherein independent from each other

R¹ is hydrogen or methoxy,R² is hydrogen, methyl or —NHCO—(C₁-C₂)-alkyl,R³ to R⁶ is hydrogen, C₁-C₂-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,

-   -   wherein    -   n is 1 or 2 and    -   m is 1 or 2,        with the proviso that at least one of R³ and R⁴ in formula (1)        and at least one of R⁵ and R⁶ in formula (2) is not hydrogen,        R¹⁰ is hydrogen or methoxy,        R¹¹ is hydrogen, methyl or —NHCO—(C₁-C₂)-alkyl,        X⁵ and X⁶ is hydrogen, bromo, chloro, nitro or cyano,        with the proviso that at least one of X⁵ and X⁶ in formula (2)        is not hydrogen.

Particularly preferred is a dye mixture as described above comprising atleast one dye of formula (1a) and at least one dye of formula (2a).

Also, particularly preferred are dye mixtures comprising:

-   -   at least one dye of formula (1a) and at least one dye of formula        (2b),    -   at least one dye of formula (1a) and at least one dye of formula        (2c),    -   at least one dye of formula (1a) and at least one dye of formula        (2d),    -   at least one dye of formula (1b) and at least one dye of formula        (2a),    -   at least one dye of formula (1b) and at least one dye of formula        (2b),    -   at least one dye of formula (1b) and at least one dye of formula        (2c),    -   at least one dye of formula (1b) and at least one dye of formula        (2d)

Most preferred is a dye mixture comprising at least one dye selectedfrom the list consisting of dyes (1-1) to (1-70) as described above andat least one dye selected from the list consisting of dyes (2-1) to(2-46).

Also preferred is a dye mixture as described above, comprising one ormore dyes selected from the group consisting of dyes of formulae (3),(4) and (5),

wherein independent from each otherX⁴ is hydrogen or nitro,Y² is (C₁-C₄)-alkyl, phenyl or (CH₂)_(m)-phenyl,Y⁴ is (C₁-C₅)-alkyl or (CH₂)_(m)-phenyl,Y⁶ is hydrogen, nitro, cyano, carboxy, (C₁-C₄)-alkyl or (C₁-C₄)-alkoxyandm is 1 to 4.

More preferred is a dye mixture as described above, comprising one ormore dyes selected from the group consisting of dyes of formulae (3),(4) and (5) wherein

X⁴ is hydrogen or nitro,Y² is (C₁-C₂)-alkyl or (CH₂)_(m)-phenyl,Y⁴ is (C₁-C₄)-alkyl or (CH₂)_(m)-phenyl,Y⁶ is hydrogen, nitro, cyano or carboxy andm is 1 or 2.

Even more preferred is a dye mixture as described above, comprising oneor more dyes selected from the group consisting of dyes of formulae (3),(4) and (5) wherein

X⁴ is hydrogen or nitro,Y² is (C₁-C₂)-alkyl or (CH₂)_(m)-phenyl,Y⁴ is (C₁-C₄)-alkyl or (CH₂)_(m)-phenyl,Y⁶ is hydrogen andm is 1 or 2.

A dye mixture as described above is particularly preferred whencomprising at least one dye of formula (3) selected from the dyesconsisting of

A dye mixture as described above is particularly preferred whencomprising at least one dye of formula (4) selected from the dyesconsisting of

A dye mixture as described above is particularly preferred whencomprising at least one dye of formula (5) selected from the dyesconsisting of

The dyes of formula (1) and (2) are known and can be prepared accordingto known procedures, for example from: WO 2016/041849 and EP 0 864 615.

The dyes of formula (3), (4) and (5) are known and can be preparedaccording to known procedures, for example from the documents: EP 0 440072, DE 19 646 429, GB 2 300 863, U.S. Pat. No. 4,140,684 and DE1544446.

A process for the production of a dye mixture as described above,comprising

-   -   a) mixing the dyes of formula (1) and (2) and optionally the        dyes of formula (3) and/or (4) and/or (5),    -   b) homogenising the mixture obtained in step a)        forms another aspect of the present invention.

The also exist preferred ranges of the amount of dyes in the mixtures:

Ranges in weight % of the dye-components of the dye mixtures asdescribed above are preferably:

Dye(s) of formula 1: 10 to 90,Dye(s) of formula 2: 90 to 10.

More preferred are:

Dye(s) of formula 1: 25 to 75,Dye(s) of formula 2: 75 to 25.

The amounts of dyes of formula (1) and of formula (2) add up to 100 wt %in those cases where no additional dyes are present in the dye mixtures.In those cases where other dyes—and preferably those selected from thedyes of formulae (3), (4) and (5)—are present, the amount of dyespreferably is as follows:

Dye(s) of formula 1: 10 to 80,Dye(s) of formula 2: 80 to 10,Other dyes: 10 to 35,where again the sum of all dyes present adds up to 100 wt %.

And more preferred:

Dye(s) of formula 1: 25 to 60,Dye(s) of formula 2: 60 to 25,Dye(s) of formula 3, 4 and/or 5: 15 to 30,where again the sum of all dyes present adds up to 100 wt %.

EXAMPLES Example 1

-   -   a) 55 parts of a dye having formula (1-14) were mixed with 45        parts of a dye of the formula (2-4). The resulting dye mixture        of the invention was mixed intensively with 100 parts of a        lignin sulfonate dispersing agent (Reax 85A) and 300 parts of        water. The pH of the mixture is adjusted with diluted Sulfuric        acid to 5, 5+/−0, 2 and the milled in a glass bead mill (0.4-0.7        mm glass beads) for 4-6 hours to a size magnitude of 0.3-5        micrometres. The milled dye mixture slurry was filtrated from        the glass beads and spray dried in a lab spray dryer (Buchi) at        120° C. inlet and 60-70° C. outlet temperature.    -   b) 1 g of the dye mixture obtained as per a) are dispersed in        100 ml of water at 40-50° C. A dyebath is prepared from 11.5 ml        of this aqueous dispersion, 57.5 ml of deionized water and 1.2        ml of buffering solution (pH 4.5) and entered with a 5 g piece        of polyester. The dyebath is heated to 130° C. and maintained at        130° C. for 45 minutes in a Werner Mathis high temperature        dyeing machine. After rinsing with water and reduction clearing,        the polyester material has a gives blue/navy dyeing with a good        build up to deep shades, good light- and very good wet-fastness.

Example 2

30 parts dye of formula (1-33) were mixed with 30 parts of a dye offormula (1-31) and with parts of a dye powder of the formula (2-23).

The resulting dye mixture of the invention was formulated usingdispersing agent and dried via spray drying according to Example 1a) andgives blue/navy dyeing's on polyester or polyester blends under thedyeing conditions according to 1b) with a good light- and very goodwet-fastness.

Example 3

54 parts dye of formula (1-1) were mixed with 22 parts of a dye offormula (2-24) and mixed with 24 parts of a dye powder of the formula(2-21)

The resulting dye mixture of the invention was formulated usingdispersing agent and dried via spray drying according to Example 1a) andgives blue/navy dyeing's on polyester or polyester blends under thedyeing conditions according to 1b) with a good light- and very goodwet-fastness.

Example 4

38 parts dye of formula (1-7) were mixed with 53 parts of a dye offormula (2-1) and 9 parts of a dye of formula (2-28).

The resulting dye mixture of the invention was formulated usingdispersing agent and dried via spray drying according to Example 1a) andgives blue/navy dyeing's on polyester or polyester blends under thedyeing conditions according to 1b) with good light- and very goodwet-fastness.

All examples of the following tables are prepared as formulations asexplained above.

Dye of 2^(nd) Dye of Dye of 2^(nd) Dye of formula formula formulaformula Ratio Shade on Example (1) (1) (2) (2) (1):(1):(2):(2) Polyester5 (1-8) — (2-1)  — 85:—:15:— Blue 6  (1-11) — (2-1)  — 28:—:72:— Blue 7(1-1) — (2-24) — 75:—:25:— Blue 8 (1-5) — (2-24) — 15:—:85:— Blue 9(1-7) — (2-41) — 50:—:50:— Blue 10 (1-3) — (2-35) — 57:—:43:— Blue 11 (1-19) — (2-37) — 34:—:66:— Blue 12  (1-12) — (2-36) — 90:—:10:— Blue13 (1-7) — (2-35) — 40:—:60:— Blue 14  (1-11) — (2-36) — 73:—:27:— Blue15  (1-11) — (2-15) — 15:—:85:— Blue 16 (1-7) — (2-36) — 55:—:45:— Blue17 (1-7) — (2-40) — 74:—:26:— Blue 18  (1-20) — (2-41) — 25:—:75:— Blue19  (1-35) — (2-23) — 44:—:56:— Blue 20  (1-14) — (2-2)  — 87:—:13:—Blue 21  (1-22) — (2-35) — 60:—:40:— Blue 22 (1-8) (1-11) (2-29) —50:40:10:— Navy 23 (1-3) — (2-24) (2-28) 60:—:22:18 Red. Navy 24 (1-3) —(2-15) (2-30) 53:—:31:16 Red. Navy 25  (1-16) — (2-1)  (2-32) 53:—:42:5Red. Navy 26 (1-8) — (2-1)  (2-31) 51:—:41:8 Red. Navy 27  (1-11) —(2-2)  (2-33) 36:—:55:9 Red. Navy 28 (1-7) (1-11) (2-1)  (2-29)28:28:34:10 Red. Navy 29 (1-3) — (2-29) — 76:—:24:— Bl. Violet 30 (1-24) — (2-28) — 66:—:34:— Violet 31  (1-33) — (2-32) — 83:—:17:— Red.Navy 32  (1-27) — (2-33) — 74:—:26:— Violet 33  (1-29) — (2-31) —69:—:31:— Violet 34  (1-11) — (2-42) — 60:—:40:— Violet 35 (1-7) —(2-42) — 50:—:50:— Violet 36 (1-3) — (2-43) — 57:—:43:— Black 37 (1-8)(1-11) (2-44) — 20:40:40:— Black 38 (1-3) — (2-15) (2-43) 40:—:31:29Black 39 (1-8) — (2-1)  (2-45) 36:—:29:35 Black 40  (1-11) — (2-1) (2-46) 35:—:31:34 Black 41 (1-7) (1-11) (2-1)  (2-44) 28:28:14:30 Black42 (1-7) (2-1)  (2-28) (2-44) 39:25:12:24 Black 43  (1-11) (2-1)  (2-28)(2-46) 35:30:9:26 Black Dye of 2^(nd) Dye of Dye of 2^(nd) Dye of Dye ofDye of Dye of formula formula formula formula formula formula formulaRatio Shade on Example (1) (1) (2) (2) (3) (4) (5)(1):(1):(2):(2):(3):(4):(5) Polyester 44 (1-16) — (2-2) — (3-1) (4-1)(5-2) 40:—:25:—:12:12:11 Black 45 (1-20) —  (2-11) — (3-3) (4-1) (5-1)14:—:51:—:9:12:14 Black 46 (1-24) — (2-3) — (3-4) (4-2) (5-1)59:—:18:—:7:8:8 Black 47 (1-31) —  (2-18) — (3-2) (4-1) (5-1)38:—:36:—:6:11:9 Black 48 (1-33) —  (2-22) — (3-1) (4-2) (5-2)45:—:20:—:15:8:12 Black 49 (1-7)  — (2-1) (2-28) (3-1) — (5-1)38:—:26:12:11:—:13 Black 50 (1-11) — (2-1) (2-28) (3-1) — (5-1)38:—:26:12:12:—:12 Black 51 (1-7)  (1-11) (2-1) (2-28) (3-1) — (5-1)25:23:22:9:13:—:8 Black 52 (1-7)  — (2-2) — (3-1) — (5-1)56:—:18:—:17:—:9 Black 53 (1-11) — (2-2) — (3-3) — (5-1)13:—:53:—:26:—:8 Black 54 (1-29) (1-49) (2-1) — (3-2) — (5-1)38:15:16:—:18:—:13 Black 55 (1-7)  —  (2-46) — (3-1) — (5-1)52:—:15:—:21:—:12 Black 56 (1-11) —  (2-44) — — — (5-1) 62:—:25:—:—:—:13Black 57 (1-7)  —  (2-43) — (3-1) — — 54:—:35:—:11:—:— Black

When the dye mixture of the present invention is used in dyeing, the dyemixture is dispersed in an aqueous medium by means of a dispersing agentand wetting agent in the usual way to prepare a dye bath for dyeing or aprinting of hydrophobic textile-fibres.

And also the use of a dye mixture as described above for dying fibres,as well as blends of such fibres forms an aspect of the presentinvention.

The synthetic textile material may preferably be selected from aromaticpolyester, especially polyethylene terephthalate, polyamide, especiallypolyhexamethylene adipamide, secondary cellulose acetate, cellulosetriacetate, and natural textile materials, especially cellulosicmaterials and wool. An especially preferred textile material is anaromatic polyester or fibre blend thereof with fibres of any of theabove mentioned textile materials. Especially preferred fibre blendsinclude those of polyester-cellulose, such as polyester-cotton, andpolyester-wool. The textile materials or blends thereof may be in theform of filaments, loose fibres, yarn or woven or knitted fabrics.

Particularly, among polyester fibres, not only ordinary polyester fibres(regular denier fibres) but also microfibres (fine denier fibres, whichare less than 0.6 denier) may be used as fibres which can successfullybe dyed with the dye mixture of the present invention.

In general all kinds of fibres can be dyed and therefore fibre andblends containing such fibre selected from the group consisting ofsynthetic fibre materials, nylon materials, nylon-6, nylon-6.6 andaramid fibres, vegetable fibres, seed fibres, cotton, organic cotton,kapok, coir from coconut husk; bast fibres, flax, hemp, jute, kenaf,ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres,bamboo; fibres from animals, wool, organic wool, silk, cashmere wool,alpaca fibre, mohair, Angora fibre as well as fur and leather materials;manufactured, regenerated and recycled fibres, cellulosic fibres; paperfibres, cellulosic regenerated fibres, viscose rayon fibres, acetate andtriacetate fibres, and Lyocell fibres comprising a dye mixture asdescribed above either in chemically and/or physically bound formforms/form another aspect of the present invention.

Typical examples of dispersing agent are lignosulphonates, naphthalenesulphonic acid/formaldehyde condensates and phenol/cresol/sulphanilicacid/formaldehyde condensates, typical examples of wetting agent arealkyl aryl ethoxylates which may be sulphonated or phosphated andtypical example of other ingredients which may be present are inorganicsalts, de-dusting agents such as mineral oil or nonanol, organic liquidsand buffers. Dispersing agents may be present at from 30 to 500% basedon the weight of the dye mixture. Dedusting agents may be used at from 0to 5% based on the weight of the dye mixture.

A process for dyeing or printing carboxamido- and/or hydroxyl-containingmaterial, comprising contacting the carboxamido- and/orhydroxyl-containing material with a dye mixture as described aboveand/or an aqueous solution as described above forms yet another aspectof the present invention.

For example, in the case of dyeing polyester fibres and fibre mixtureproducts such as blended yarn fabrics of union cloth product comprisingpolyester fibres can be dyed with good colour fastness by common dyeingmethods, such as a high temperature dyeing method, a carrier dyeingmethod and a thermosol dyeing method. In some cases, the addition of anacid substance to the dye bath may result in even more successfuldyeing.

Suitable process conditions may be selected from the following

-   -   (i) exhaust dyeing at a pH of from 4 to 8.5, at a temperature of        from 125 to 140° C. for from to 120 minutes and under a pressure        of from 1 to 2 bar, a sequestrant optionally being added;    -   (ii) continuous dyeing at a pH of from 4 to 8.5, at a        temperature of from 190 to 225° C. for from 15 seconds to 5        minutes, a migration inhibitor optionally being added;    -   (iii) direct printing at a pH of from 4 to 6.5, at a temperature        of from 160 to 185° C. for from 4 to 15 minutes for high        temperature steaming, or at a temperature of from 190 to 225° C.        for from 15 seconds to 5 minutes for bake fixation with dry heat        or at a temperature of from 120 to 140° C. and 1 to 2 bar for        from 10 to 45 minutes for pressure steaming, wetting agents and        thickeners (such as alginates) of from 5 to 100% by weight of        the dye optionally being added;    -   (iv) discharge printing (by padding the dye on to the textile        material, drying and overprinting) at a pH of from 4 to 6.5,        migration inhibitors and thickeners optionally being added;    -   (v) carrier dyeing at a pH of from 4 to 7.5, at a temperature of        from 95 to 100° C. using a carrier such as methylnaphthalene,        diphenylamine or 2-phenylphenol, sequestrants optionally being        added; and    -   (vi) atmospheric dyeing of acetate, triacetate and nylon at a pH        of from 4 to 7.5, at a temperature of about 85° C. for acetate        or at a temperature of about 90° C. for triacetate and nylon for        from 15 to 90 minutes, sequestrants optionally being added.

In all the above processes, the dye mixture is applied as a dispersioncomprising from 0.001 to 20 wt. %, preferably from 0.005 to 16 wt. %, ofthe dye mixture in an aqueous medium.

In addition to the above-mentioned application processes, the dyemixture may be applied to synthetic textile materials and fibre blendsby ink-jet printing, the substrates optionally having been pre-treatedto aid printing.

An ink for digital textile printing, comprising a dye mixture asdescribed above is another aspect of the present invention.

For ink-jet applications, the application medium may comprise water anda water-soluble organic solvent, preferably in a weight ratio of 1:99 to99:1, more preferably 1:95 to 50:50 and especially in the range 10:90 to40:60. The water-soluble organic solvent preferably comprises aC₁-C₄-alkanol, especially methanol or ethanol, a ketone, especiallyacetone or methyl ethyl ketone, 2-pyrrolidone or N-methylpyrrolidone, aglycol, especially ethylene glycol, propylene glycol, trimethyleneglycol, butane-2,3-diol, thiodiglycol or diethylene glycol, a glycolether, especially ethylene glycol monomethyl ether, propylene glycolmonomethyl ether or diethylene glycol monomethyl ether, urea, asulphone, especially bis-(2-hydroxyethyl) sulphone or mixtures thereof.

The dyestuff may also be applied to textile materials usingsupercritical carbon dioxide, in which case the dye formulating agentsmay optionally be omitted.

1. A dye mixture comprising at least one dye of formula (1)

wherein independent of each other R¹ is hydrogen, (C₁-C₄)-alkyl orC₁-C₄-alkoxy, R² is hydrogen, carboxy, (C₁-C₄)-alkyl, halogen,acylamino, —NHCO-aryl, —NHCO-benzyl) or sulfonylamino, R³ and R⁴ ishydrogen, (C₁-C₄)-alkyl, (CH₂)_(n)-phenyl, CH₂—CH═CH₂, (CH₂)_(n)—OH,(CH₂)_(n)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O-phenyl, (CH₂)_(n)—O-benzyl,(CH₂)_(n)—O—(CH₂)_(m)—OH, (CH₂)_(n)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl,(CH₂)_(n)—O—(CH₂)_(m)—O-phenyl, (CH₂)_(n)—O—(CH₂)_(m)—O-benzyl,(CH₂)_(n)—COOH, (CH₂)_(n)—COO—(C₁-C₄)-alkyl, (CH₂)_(n)—COO-phenyl,(CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₄)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, CHR⁹—(CH₂)_(p)—(C₁-C₄)-alkyl,CHR⁹—(CH₂)_(p) phenyl, CHR⁹—CH═CH₂, CHR⁹—(CH₂)_(p)—OH,CHR⁹—(CH₂)_(p)—O—(C₁-C₄)-alkyl, CHR⁹—(CH₂)_(p)—O-phenyl,CHR⁹—(CH₂)_(p)—O-benzyl, CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—OH,CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl,CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl, CHR⁹—(CH₂)_(p)—COOH,CHR⁹—(CH₂)_(p)—COO—(C₁-C₄)-alkyl, CHR⁹—(CH₂)_(p)—COO-phenyl,CHR⁹—(CH₂)_(p)—COO-benzyl, CHR⁹—(CH₂)_(p)—CN,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,CHR⁹—(CH₂)_(p)—O—CO—(C₁-C₄)-alkyl, CHR⁹—(CH₂)_(p)—O—CO-phenyl,CHR⁹—(CH₂)_(p)—O—CO-benzyl, CHR⁹—(CH₂)_(p)-2-furfuryl orCHR⁹—(CH₂)_(p)—O—(CH₂)_(n)-2-furfuryl, wherein R⁹ is (C₁-C₄)-alkyl or(C₁-C₄)-alkyl substituted by —OH or halogen, n is 1 to 4, m is 1 to 4and p is 0 to 3, with the proviso that at least one of R³ and R⁴ is nothydrogen, and at least one dye of formula (2)

wherein independent of each other R⁵ and R⁶ is hydrogen, (C₁-C₄)-alkyl,(CH₂)_(n)-phenyl, CH₂—CH═CH₂, (CH₂)_(n)—OH, (CH₂)_(n)—O—(C₁-C₄)-alkyl,(CH₂)_(n)—O-phenyl, (CH₂)_(n)—O-benzyl, (CH₂)_(n)—O—(CH₂)_(m)—OH,(CH₂)_(n)—O—(CH₂)_(m)—O—(C₁-C₄)-alkyl, (CH₂)_(n)—O—(CH₂)_(m)—O-phenyl,(CH₂)_(n)—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COOH,(CH₂)_(n)—COO—(C₁-C₄)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₄)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₄)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl or(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, wherein n is 1 to 4 and m is 1 to 4,with the proviso that at least one of R⁵ and R⁶ is not hydrogen, R¹⁰ ishydrogen, (C₁-C₄)-alkyl or (C₁-C₄)-alkoxy, R¹¹ is hydrogen, carboxy,(C₁-C₄)-alkyl, halogen, acylamino, —NHCO-aryl, —NHCO-benzyl) orsulfonylamino, X⁵ and X⁶ is hydrogen, halogen, nitro or cyano, with theproviso that at least one of X⁵ and X⁶ is not hydrogen.
 2. The dyemixture according to claim 1, wherein independent of each other in theat least one dye of formula (1) R¹ is hydrogen, methyl or methoxy, R² ishydrogen, hydroxy, COOH, COO—(C₁-C₂)-alkyl, (C₁-C₂)-alkyl,—NHCO—(C₁-C₂)-alkyl, —NHCO-aryl, —NHCO-benzyl or —NHSO₂—(C₁-C₂)-alkyl,R³ and R⁴ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)₂—O—(CH₂)_(m)—O-phenyl,(CH₂)₂—O—(CH₂)_(m)—O-benzyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl,(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, CHR⁹—CH═CH₂,CHR⁹—(CH₂)_(p)—O—(C₁-C₂)-alkyl, CHR⁹—(CH₂)_(p)—O-phenyl,CHR⁹—(CH₂)_(p)—O-benzyl, CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O-phenyl,CHR⁹—(CH₂)_(p)—O—(CH₂)_(m)—O-benzyl, CHR⁹—(CH₂)_(p)—COO—(C₁-C₂)-alkyl,CHR⁹—(CH₂)_(p)—COO-phenyl, CHR⁹—(CH₂)_(p)—COO-benzyl, CHR⁹—(CH₂)_(p)—CN,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO-phenyl,CHR⁹—(CH₂)_(p)—COO(CH₂)_(m)—CO-benzyl,CHR⁹—(CH₂)_(p)—O—CO—(C₁-C₂)-alkyl, CHR⁹—(CH₂)_(p)—O—CO-phenyl orCHR⁹—(CH₂)_(p)—O—CO-benzyl, wherein R⁹ is (C₁-C₄)-alkyl or (C₁-C₄)-alkylsubstituted by —OH or halogen, n is 1 or 2, m is 1 or 2 and p is 0 or 1,with the proviso that at least one of R³ and R⁴ is not hydrogen.
 3. Thedye mixture according to claim 1, wherein independent of each other inthe at least one dye of formula (1) R¹ is hydrogen or methoxy, R² ishydrogen, methyl or —NHCO—(C₁-C₂)-alkyl, R³ and R⁴ is hydrogen,(C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl,(CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl, (CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,(CH₂)_(n)—COO—(C₁-C₂)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl,CHR⁹—(CH₂)_(p)—COO—(C₁-C₂)-alkyl, wherein R⁹ is (C₁-C₄)-alkyl, n is 1 or2, m is 1 or 2 and with the proviso that at least one of R³ and R⁴ isnot hydrogen.
 4. The dye mixture according to claim 1, wherein the atleast one dye of formula (1) is a dye of formula (1a)

wherein independent from each other R³ and R⁴ is hydrogen,(C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl,(CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl, (CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,(CH₂)_(n)—COO—(C₁-C₂)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl orCHR⁹—(CH₂)_(p)—COO—(C₁-C₂)-alkyl, wherein R⁹ is (C₁-C₄)-alkyl, n is 1 or2, m is 1 or 2 and p is 0 or 1, with the proviso that at least one of R³and R⁴ is not hydrogen and R⁷ and R⁸ is ethyl or methyl.
 5. The dyemixture according to claim 1, wherein the at least one dye of formula(1) is a dye of formula (1b)

wherein independent from each other R³ and R⁴ is hydrogen,(C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl,(CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl, (CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,(CH₂)_(n)—COO—(C₁-C₂)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl orCHR⁹—(CH₂)_(p)—COO—(C₁-C₂)-alkyl, wherein R⁹ is (C₁-C₄)-alkyl, n is 1 or2 and m is 1 or 2, p is 0 or 1, with the proviso that at least one of R³and R⁴ is not hydrogen and R⁷ is ethyl or methyl.
 6. The dye mixtureaccording to claim 1, wherein the at least one dye of formula (1) is adye of formula (1c)

wherein independent from each other R³ and R⁴ is hydrogen,(C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl,(CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl, (CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,(CH₂)_(n)—COO—(C₁-C₂)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl, (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl orCHR⁹—(CH₂)_(p)—COO—(C₁-C₂)-alkyl, wherein R⁹ is (C₁-C₄)-alkyl, n is 1 or2, m is 1 or 2 and p is 0 or 1, with the proviso that at least one of R³and R⁴ is not hydrogen.
 7. The dye mixture according to claim 1, whereinthe at least one dye of formula (1) is selected from the groupconsisting of


8. The dye mixture according to claim 1, wherein independent of eachother in the at least one dye of formula (2) R⁵ and R⁶ is hydrogen,(C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl,(CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl, (CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,(CH₂)₂—O—(CH₂)_(m)—O-phenyl, (CH₂)₂—O—(CH₂)_(m)—O-benzyl,(CH₂)_(n)—COO—(C₁-C₂)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,(CH₂)_(n)—O—CO-benzyl, COO—(CH₂)_(n)-2-furfuryl or(CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, wherein n is 1 or 2 and m is 1 or 2,with the proviso that at least one of R⁵ and R⁶ is not hydrogen, R¹⁰ ishydrogen, methyl or methoxy, R¹¹ is hydrogen, hydroxy, COOH,COO—(C₁-C₂)-alkyl, (C₁-C₂)-alkyl, —NHCO—(C₁-C₂)-alkyl, —NHCO-aryl,—NHCO-benzyl or —NHSO₂—(C₁-C₂)-alkyl and X⁵ and X⁶ is hydrogen, chloro,bromo, nitro or cyano, with the proviso that at least one of X⁵ and X⁶is not hydrogen.
 9. The dye mixture according to claim 1, whereinindependent of each other in the at least one dye of formula (2) R⁵ andR⁶ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, wherein nis 1 or 2 and m is 1 or 2, with the proviso that at least one of R⁵ andR⁶ is not hydrogen, R¹⁰ is hydrogen or methoxy, R¹¹ is hydrogen, methylor —NHCO—(C₁-C₂)-alkyl and X⁵ and X⁶ is hydrogen, bromo, chloro, nitroor cyano, with the proviso that at least one of X⁵ and X⁶ is nothydrogen.
 10. The dye mixture according to claim 1, wherein the at leastone dye of formula (2) is a dye of formula (2a)

wherein independent from each other R⁵ and R⁶ are hydrogen,(C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl,(CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl, (CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,(CH₂)_(n)—COO—(C₁-C₂)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, wherein nis 1 or 2 and m is 1 or 2, with the proviso that at least one of R⁵ andR⁶ is not hydrogen, R⁷ and R⁸ is ethyl or methyl, X⁵ is hydrogen, bromo,chloro, nitro or cyano and X⁶ is nitro or cyano, with the proviso thatX⁵ and X⁶ are not both nitro.
 11. The dye mixture according to claim 1,wherein the at least one dye of formula (2) is a dye of formula (2b)

R⁵ and R⁶ are hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂,(CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, wherein nis 1 or 2 and m is 1 or 2, with the proviso that at least one of R⁵ andR⁶ is not hydrogen, R⁷ is ethyl or methyl and X⁵ is bromo, chloro, nitroor cyano and X⁶ is nitro or cyano, with the proviso that X⁵ and X⁶ arenot both nitro.
 12. The dye mixture according to claim 1, wherein the atleast one dye of formula (2) is a dye of formula (2c)

wherein independent from each other R² is hydrogen or—NHCO—(C₁-C₂)-alkyl, R⁵ and R⁶ is hydrogen, (C₁-C₂)-alkyl, (CH₂)-phenyl,CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl, (CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl,(CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl, (CH₂)_(n)—COO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl, (CH₂)_(n)—CN,(CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, wherein nis 1 or 2 and m is 1 or 2 with the proviso that at least one of R⁵ andR⁶ is not hydrogen, X⁵ and X⁶ is bromo or chloro.
 13. The dye mixtureaccording to claim 1, wherein the at least one dye of formula (2) is adye of formula (2d)

wherein independent from each other R⁵ and R⁶ is hydrogen,(C₁-C₂)-alkyl, (CH₂)-phenyl, CH₂—CH═CH₂, (CH₂)₂—O—(C₁-C₂)-alkyl,(CH₂)₂—O-phenyl, (CH₂)₂—O-benzyl, (CH₂)₂—O—(CH₂)_(m)—O—(C₁-C₂)-alkyl,(CH₂)_(n)—COO—(C₁-C₂)-alkyl, (CH₂)_(n)—COO-phenyl, (CH₂)_(n)—COO-benzyl,(CH₂)_(n)—CN, (CH₂)_(n)—COO(CH₂)_(m)—CO—(C₁-C₂)-alkyl,(CH₂)_(n)—COO(CH₂)_(m)—CO-phenyl, (CH₂)_(n)—COO(CH₂)_(m)—CO-benzyl,(CH₂)_(n)—O—CO—(C₁-C₂)-alkyl, (CH₂)_(n)—O—CO-phenyl,COO—(CH₂)_(n)-2-furfuryl or (CH₂)_(m)—O—(CH₂)_(n)-2-furfuryl, wherein nis 1 or 2 and m is 1 or 2 with the proviso that at least one of R⁵ andR⁶ is not hydrogen, R⁷ is ethyl or methyl and X⁶ is chloro, bromo, nitroor cyano.
 14. The dye mixture according to claim 1, wherein the at leastone dye of formula (2) is selected from the group consisting of